USOO6933353B2 (12) United States Patent (10) Patent No.: US 6,933,353 B2 Wan 45) Date of Patent: Aug. 23,9 2005 (54) OLEFIN POLYMERIZATION PROCESS 6,489,408 B2 12/2002 Mawson et al. .............. 526/68 6,524.986 B2 2/2003 Costa et al. .......... ... 502/109 (75) Inventor: Shaotian Wang, Mason, OH (US) 6,541,583 B2 4/2003 Meverden et al. .......... 526/127 6,559,251 B1 * 5/2003 Wang et al. .......... ... 526/127 (73) Assignee: Equistar Chemicals, LP, Houston, TX 6,765,074 B2 7/2004 Sartain ....................... 526/153 (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO O1/53360 5/1999 patent is extended or adjusted under 35 WO WO 99/24446 7/2001 U.S.C. 154(b) by 92 days. OTHER PUBLICATIONS (21) Appl. No.: 10/614,615 Soga et al., Macromolecules 27 (1994) 7938–7940. Buu-Hoi and Xuong, J. Chem. Soc. (1952) 2225. (22) Filed: Jul. 7, 2003 Jingling et al., J. Organometal. Chem. 460 (1993) 191. (65) Prior Publication Data Noh, et al., J. Organometal. Chem, 518 (1996) 1. Noh, et al., J. Organometal. Chem, 580 (1999) 90. US 2005/0010004 A1 Jan. 13, 2005 * cited by examiner (51) Int. Cl. ............................... C08F 4/44; CO8F 4/52 (52) U.S. Cl. ....................... 526/114; 526/116; 526/161; Primary Examiner-David W. Wu 526/172; 526/148; 526/151; 526/130; 526/129; ASSistant Examiner-Rip A. Lee 526/348.5; 526/348.4; 526/348.6; 526/351; (74) Attorney, Agent, or Firm- John Tyrell; Jonathan L. 526/352; 526/348.2 Schuchardt (58) Field of Search ................................. 526/114, 116, (57) ABSTRACT 526/172, 161, 113, 126,901, 943 A method for preparing a Supported organometallic complex (56) References Cited is disclosed. An organometallic complex is combined with a U.S. PATENT DOCUMENTS Support material that has been treated with an organozinc compound. The organometallic complex comprises a Group 4,370,456 A * 1/1983 George ....................... 502/110 3 to 10 transition metal and an indenoindolyl ligand that is 6,177,527 B1 1/2001 Sishta et al. ................ 526/134 bonded to the transition metal. Also disclosed is a proceSS 6.211,311 B1 4/2001 Wang et al. ................ 526/1.31 for polymerizing an olefin using the Supported complex. 6,221,802 B1 4/2001 Costa et al. ................ 502/109 Organozinc treatment of the Support unexpectedly boosts 6,440,8896,232.260 B1 8/20025/2001 TsuieNagy et.......................... al. ................. 502/155... catalyst activity and polyolefin molecular weight. 6,451,724 B1 9/2002 Nifant’ev et al. ........... 502/103 6,476,173 B1 11/2002 Lin et al. .................... 526/351 21 Claims, No Drawings US 6,933,353 B2 1 2 OLEFIN POLYMERIZATION PROCESS They State that it is preferred not to use a Support, but give a long list of possible Supports including Silica with dieth ylzinc. No further teachings are found nor are the catalysts FIELD OF THE INVENTION used based upon indenoindolyl Systems. This invention relates to a process for polymerizing an Despite the considerable work that has been done with olefin with an activator and a Supported organometallic catalysts based upon indenoindolyl ligands there is a need complex. The proceSS gives improved catalyst activity and for improvement, especially with regard, to increasing activ polyolefins with increased molecular weight. ity and molecular weight. Organozinc compounds have apparently not been used in conjunction with organometallic BACKGROUND OF THE INVENTION complexes that incorporate indenoindolyl ligands. When Many olefin polymerization catalysts are known, includ organozinc compounds are mentioned for use in olefin ing conventional Ziegler-Natta catalysts. While these cata polymerizations with metallocene catalysts they act as chain lysts are inexpensive, they exhibit low activity and are transfer agents and reduce polyolefin molecular weight, the generally poor at incorporating C-olefin comonomers. To opposite of the effect I have found with complexes contain improve polymer properties, Single-site catalysts, in particu 15 ing indenoindolyl ligands. lar metallocenes are beginning to replace Ziegler-Natta catalysts. SUMMARY OF THE INVENTION Catalyst precursors that incorporate a transition metal and an indenoindolyl ligand are known. U.S. Pat. Nos. 6,232,260 In one aspect, the invention is a method for preparing a and 6,451,724 disclose the use of transition metal catalysts Supported organometallic complex. An organometallic com based upon indenoindolyl ligands, but have no examples pleX is combined with a Support material that has been using Supported catalysts. While they mention that Sup treated with an organozinc compound. The organometallic ported catalysts may be used, little information is given complex comprises a Group 3 to 10 transition metal and an about the preparation of the Supported catalysts. 25 indenoindolyl ligand that is bonded to the transition metal. WO 01/53360 discloses open architecture indenoindolyl In another aspect, the invention is a process for polymer catalysts that may be Supported. In the Single example izing an olefin. The Supported organometallic complex (Example 8) preparing a Supported catalyst, a Solution of the described above is mixed with an activator and an olefin, and catalyst is added to a polyethylene Support. the olefin is polymerized. Pretreatment of the support with U.S. Pat. No. 6,559,251 discloses a process for polymer an organozinc compound combined with the use of an izing olefins with a Silica-Supported, indenoindolyl Group indenoindolyl transition metal complex provides an unex 4-6 transition metal complex having open architecture. pected boost in both catalyst activity and polyolefin molecu U.S. Pat. No. 6,541,583 discloses a process for polymer lar weight. izing propylene in the presence of a Group 3–5 transition metal catalyst that has two non-bridged indenoindolyl ligands. None of the examples uses a Supported catalyst. 35 DETAILED DESCRIPTION OF THE They state that the catalyst can be immobilized on a Support INVENTION but give no process details. The invention includes a method for preparing a Sup U.S. Pat. No. 6,211,311 prepares supported catalysts ported organometallic complex. The complex contains a containing heteroatomic ligands. The Support is chemically Group 3 to 10 transition metal. Preferably the transition modified with an organoaluminum, organosilicon, organo 40 metal is a Group 3–5 transition metal, more preferably a magnesium or organoboron compound for improved cata Group 4 transition metal. Most preferably, the transition lyst Stability and activity. There is no indication that Zinc metal is Zirconium. compounds may be used, and there is no indication that increased polymer molecular weight may be obtained. The organometallic complex contains at least one inde 45 noindolyl ligand bonded to the transition metal. “Indenoin Pending application Ser. No. 10/123,774, filed Apr. 16, dolyl” ligands are conveniently generated by deprotonating 2002, discloses a process for polymerizing ethylene in the an indenoindole compound using a potent base. By “inde presence of a Silica-Supported Group 3-10 transition metal noindole compound, we mean an organic compound that catalyst that has two bridged indenoindolyl ligands. This has both indole and indene rings. The five-membered rings application teaches that the Silica can be chemically treated from each are fused, i.e., they share two carbon atoms. The and points to the above-mentioned U.S. Pat. No. 6,211,311. 50 rings can be fused Such that the indole nitrogen and the only Organozinc compounds Such as diethylzinc have been sp-hybridized carbon on the indenyl ring are “trans” to each used in olefin polymerizations as chain transfer agents to other. Such is the case in an indeno1,2-bindole ring System lower molecular weight. For example, U.S. Pat. Nos. 6,524, Such as: 986; 6,489,408; 6,476,173 and 6,221,802 mention the use of diethylzinc to control molecular weight by acting as a chain 55 transfer agent Similarly to how hydrogen is often used to lower molecular weight. None teaches treatment of a Support with an organozinc compound prior to combining it with an organometallic complex. Macromolecules 27 7938–7940 (1994) teaches polymer 60 ization of methyl methacrylate by dicyclopentadienyldim ethyl Zirconium by reacting the methyl methacrylate with diethylzinc prior to unsupported catalyst addition and poly merization. Suitable ring Systems also include those in which the U.S. Pat. No. 6,177.527 teaches an olefin polymerization 65 indole nitrogen and the sp-hybridized carbon of the indene proceSS using racemic and meSO Stereoisomers of a metal are beta to each other, i.e., they are on the same Side of the locene catalyst containing two cycloalkadienyl ligands. molecule. This is an indeno2,1-bindole ring System: US 6,933,353 B2 4 arylene, diarylene, polyarylene, cycloalkyl, adamantyl, aralkylene, alkenyl, and alkynyl. Specific examples of Suit able divalent linking groups are methylene, 1,2-ethenyl, 1,2-ethynyl, isopropylidene, 1,4-phenylene, C.C.'-xylyl, 4,4'- biphenylene, 1,3-adamantyl, 1,4-adamantyl, phenylboranyl, methylboranyl, dimethylsilyl, diphenylsily 1, b is (dimethylsilyl), oxybis(dimethylsilyl), and the like. These and other divalent linking groups are described in the background references. (For Some examples, see J. Orga nometal. Chem. 460 (1993) 191; 518 (1996) 1; 580 (1999) 90.) The ring atoms can be unsubstituted or substituted with The divalent linking group can link the indenoindolyl one or more groups Such as alkyl, aryl, aralkyl, halogen, ligand to a polymerization-stable ligand. Suitable Sillyl, nitro, dialkylamino, diarylamino, alkoxy, aryloxy, polymerization-stable ligands include cyclopentadienyl, thioether, or the like. Additional fused rings can be present, indenyl, fluorenyl, boraaryl, indenoindolyl, and the like. as long as an indenoindole moiety is present. 15 Bridged indenoindolyl ligands also include those used in Numbering of indenoindoles follows IUPAC Rule A-22.